Method for producing alkoxylated products at optimized reaction pressures

ABSTRACT

The present invention relates to a process for the preparation of at least one alkoxylate comprising the bringing into contact of an alkylene oxide mixture at least comprising ethylene oxide with at least one starter compound in the presence of at least one double-metal cyanide compound, where, during the induction phase, the sum of inert gas partial pressure and ethylene oxide partial pressure is 1.5 bar to 6.0 bar, to the alkoxylates obtainable by such a process, and to the use of such alkoxylates as emulsifier, foam regulator or as wetting agent for hard surfaces.

The present invention relates to a process for the preparation of atleast one alkoxylate comprising the bringing into contact of an alkyleneoxide mixture at least comprising ethylene oxide with at least onestarter compound in the presence of at least one double-metal cyanidecompound where, during the induction phase, the sum of inert gas partialpressure and ethylene oxide partial pressure is 1.5 bar to 6.0 bar, tothe alkoxylates obtainable by such a process, and to the use of suchalkoxylates as emulsifier, foam regulator or as wetting agent for hardsurfaces.

It is known from the literature that double-metal cyanide compounds (DMCcompounds) can be used as catalysts for the reaction of startermolecules having active hydrogen and alkylene oxides, for example in apolymerization reaction. The ring-opening polymerizations of alkyleneoxides is described, for example, in EP-A 0 892 002, EP-A 1 0 862 977and in EP-A 0 755 716. In the polymerization of alkylene oxides, DMCcompounds have a high activity as catalyst.

Processes for the alkoxylation of aliphatic alcohols and the resultingalkoxylates are known in principle from the prior art. WO 01/04183, forexample, describes a process for the ethoxylation of hydroxy-functionalstarter compounds which is carried out in the presence of a double-metalcyanide compound as catalyst.

Alkoxylates of aliphatic alcohols are used widely as surfactants,emulsifiers or foam suppressors. The wetting and emulsifying propertiesdepend heavily on the nature of the alcohol and the nature and amount ofthe alkoxide adducts.

WO 94/11330 relates to alkoxylates of 2-propylheptanol and their use. Inthe alkoxylates, 2-propylheptanol reacted firstly with 1 to 6 mol ofpropylene oxide and then with 1 to 10 mol of ethylene oxide in thepresence of alkali metal hydroxides as catalyst is present. In theexamples, 2-propylheptanol reacted firstly with 4 mol of propylene oxideand then 6 mol of ethylene oxide is used. It is stated that the alkyleneoxide adducts exhibit an improved relationship of foaming behavior todetergency effect. In addition, it is stated that the alkoxylatesexhibit good wetting behavior. They are used in detergent compositionsfor the cleaning of textile materials. WO 94/11331 relates to the use ofsuch alkoxylates.

U.S. Pat. No. 2,508,036 likewise relates to the use of2-n-propylheptanol ethoxylates which contain 5 to 15 mol of ethyleneoxide as wetting agents in aqueous solutions. It is stated that theproducts can be used as surfactants in detergents.

DE 102 18 754 and DE 102 18 753 relate to the use of C₁₀-alkanolalkoxylate mixtures, in particular alkanol ethoxylate mixtures, suchC₁₀-alkanol alkoxylate mixtures and processes for their preparation. DE102 18 752 likewise describes alkoxylate mixtures and detergentscomprising these and also processes for the preparation of thealkoxylate mixtures and the use of the detergent for the washing orcleaning of textiles.

During the alkoxylation, in particular the ethoxylation, of startercompounds in the presence of double-metal cyanide compounds, twoproblems in particular arise. Firstly, the induction phase of thereaction is sometimes very long, which leads to an extension of thereaction times and to increased costs, and secondly the activity of thecatalyst during the reaction often slowly decreases until the reactionrate is no longer adequate.

It is an object of the invention to provide a process for theethoxylation of starter compounds with improved conversion of thestarter compound, shortened induction phase and improved catalyststability.

We have found that this object is achieved according to the invention bya process for the preparation of at least one alkoxylate comprising thebringing into contact of an alkylene oxide mixture at least comprisingethylene oxide with at least one starter compound in the presence of atleast one double-metal cyanide compound of the formula I:M¹ _(a)[M²(CN)_(b)(A)_(c)]_(d)·fM¹ _(g)X_(n)·h(H₂O)·eL·kP   (I)

-   -   in which        -   M¹ is at least one metal ion chosen from the group            consisting of Zn²⁺, Fe²⁺, Fe³⁺, Co³⁺, Ni²⁺, Mn²⁺, Co²⁺,            Sn²⁺, Pb²⁺, Mo⁴⁺, Mo⁶⁺, Al³⁺, V⁴⁺, V⁵⁺, Sr²⁺, W⁴⁺, W⁶⁺,            Cr²⁺, Cr³⁺, Cd²⁺, Hg²⁺, Pd²⁺, Pt²⁺, V²⁺, Mg²⁺, Ca²⁺, Ba²⁺,            Cu²⁺, La³⁺, Ce³⁺, Ce⁴⁺, Eu³⁺, Ti³⁺, Ti⁴⁺, Ag⁺, Rh²⁺, Rh³⁺,            Ru²⁺, Ru³⁺,        -   M² is at least one metal ion chosen from the group            consisting of Fe²⁺, Fe³⁺, Co²⁺, C³⁺, Mn²⁺, Mn³⁺, V⁴⁺, V⁵⁺,            Cr²⁺, Cr³⁺, Rh³⁺, Ru²⁺, Ir³⁺,        -   A and X, independently of one another, are an anion chosen            from the group consisting of halide, hydroxide, sulfate,            carbonate, cyanide, thiocyanate, isocyanate, cyanate,            carboxylate, oxalate, nitrate, nitrosyl, hydrogensulfate,            phosphate, dihydrogenphosphate, hydrogenphosphate or            hydrogencarbonate,        -   L is a water-miscible ligand chosen from the group            consisting of alcohols, aldehydes, ketones, ethers,            polyethers, esters, polyesters, polycarbonate, ureas,            amides, primary, secondary and tertiary amines, ligands with            pyridine nitrogen, nitriles, sulfides, phosphides,            phosphites, phosphines, phosphonates and phosphates,        -   k is a fraction or integer greater than or equal to zero,            and        -   P is an organic additive,        -   a, b, c, d, g and n are chosen such that the            electroneutrality of the compound (I) is ensured, where c            may be 0,        -   e is the number of ligand molecules, a fraction or integer            greater than 0, or 0,        -   f and h, independently of one another, are a fraction or            integer greater than 0, or 0,

wherein, during the induction phase, the sum of inert gas partialpressure and ethylene oxide partial pressure is 1.5 bar to 6.0 bar.

Induction phase is understood as meaning that the alkoxylation reactiondoes not start immediately after the bringing into contact of thealkylene oxide with the starter alcohol and the double-metal cyanidecompound, but is delayed by a certain time. This induction phase isevident, for example, from the fact that, after a small amount ofalkylene oxide has been metered in, a certain pressure results in thereactor which remains constant for a certain time and rapidly decreasesat the end of the induction phase. Following the pressure drop, thereaction has started, and the further metered addition of the alkyleneoxide can take place.

According to the invention, the sum of inert gas partial pressure andethylene oxide partial pressure during the induction phase is 1.5 to 6.0bar, preferably 1.5 to 5.0 bar, particularly preferably 1.5 to 3.0 bar.This pressure range is particularly advantageous since on the one hand arapid start-up of the reaction is observed, but on the other hand thepressure is not too high. The total pressure is made up of the partialpressures of the individual gases. If only inert gas and ethylene oxideare used, the sum of inert gas partial pressure and ethylene oxidepartial pressure corresponds to the total pressure. A high totalpressure at the start of the reaction would, for example, requireexpensive reaction vessels and thus make the overall process moreexpensive.

In a preferred embodiment, in the process according to the invention,firstly the reactor is charged with an inert gas and then the alkyleneoxide mixture comprising at least ethylene oxide is added. The inert gaspartial pressure is, according to the invention, for example 1.5 to 6.0bar, preferably 1.5 bar to 3.0 bar, preferably 1.5 to 2.5 bar,particularly preferably 1.5 to 2.0 bar.

For the purposes of the present invention, the ethylene oxide partialpressure is less than or equal to the inert gas partial pressure, wherethe sum of inert gas partial pressure and ethylene oxide partialpressure is 1.5 bar to 6.0 bar.

This procedure has the advantage that using the inert gas a partialpressure can be established and then the alkylene oxide mixture at leastcomprising ethylene oxide can be metered in, where the ethylene oxideconcentration in the gas phase is not too high. For safety reasons, aconcentration of >40%, preferably >50%, of ethylene oxide in the gasphase should be avoided in the reactor since high concentrations mayresult in spontaneous EO decomposition and thus to overheating orexplosion of the reactor.

The ethylene oxide partial pressure is determined in the case of such aprocedure essentially through the ratio of the metered addition ofethylene oxide and of the reaction rate of the ethylene oxide. For thepurposes of the present invention, the ethylene oxide partial pressureduring the induction phase is preferably less than 3.0 bar, inparticular less than 1.5 bar, for example less than 1.0 bar.

In the process according to the invention, the reaction vessel can, forexample, firstly be filled with a suspension of alcohol and DMCcatalyst. The catalyst can then be activated by separating off water,e.g. by heating and/or evacuating the reaction vessel.

The reaction mixture is then advantageously heated to reactiontemperature and a nitrogen prepressure is established. In the furthercourse of the process, a starting amount of ethylene oxide, for example,is metered in. After the reaction has started, further ethylene oxide ismetered in, the reaction mixture is stirred until all of the ethyleneoxide has reacted. The reaction mixture can optionally be worked upfurther.

In a preferred embodiment, the present invention therefore provides aprocess where, during the induction phase, the inert gas partialpressure is 1.5 bar to 6.0 bar, preferably 1.5 to 3.0 bar. For thepurposes of the present invention, suitable inert gases are, forexample, nitrogen, CO₂ or noble gases such as argon or mixtures thereof,preferably nitrogen.

According to the invention, the pressure changes during the reaction.Following a possible initial pressure drop as the reaction starts, thepressure increases over the course of the reaction since the fill levelin the reactor increases and the gas mixture is compressed. According tothe invention, it is preferred that the total pressure, in particularthe sum of inert gas partial pressure and ethylene oxide partialpressure, in the course of the reaction does not exceed 20 bar, forexample does not exceed 11 bar, preferably does not exceed 6 bar, inparticular does not exceed 3.5 bar.

In a preferred embodiment, the present invention therefore provides aprocess where the total pressure does not exceed 11 bar in the course ofthe reaction.

The process according to the invention is carried out at temperatures offrom 80 to 190° C.

The process according to the invention for the preparation of analkoxylate is carried out in the presence of a double-metal cyanidecompound of the formula I as catalyst:M ¹ _(a)[M²(CN)_(b)(A)_(c)]_(d)·fM¹ _(g)X_(n)·h(H₂O)·eL·kP   (I)

-   -   in which        -   M¹ is at least one metal ion chosen from the group            consisting of Zn²⁺, Fe²⁺, Fe³⁺, Co³⁺, Ni²⁺, Mn²⁺, Co²⁺,            Sn²⁺, Pb²⁺, Mo⁴⁺, Mo⁶⁺, Al³⁺, V⁴⁺, V⁵⁺, Sr²⁺, W⁴⁺, W⁶⁺,            Cr²⁺, Cr³⁺, Cd²⁺, Hg²⁺, Pd²⁺, Pt²⁺, V²⁺, Mg²⁺, Ca²⁺, Ba²⁺,            Cu²⁺, La³⁺, Ce³⁺, Ce⁴⁺, Eu³⁺, Ti³⁺, Ti⁴⁺, Ag⁺, Rh²⁺, Rh³⁺,            Ru²⁺, Ru³⁺,        -   M² is at least one metal ion chosen from the group            consisting of Fe²⁺, Fe³⁺, Co²⁺, Co³⁺, Mn²⁺, Mn³⁺, V⁴⁺, V⁵⁺,            Cr²⁺, Cr³⁺, Rh³⁺, Ru²⁺, Ir³⁺,        -   A and X, independently of one another, are an anion chosen            from the group consisting of halide, hydroxide, sulfate,            carbonate, cyanide, thiocyanate, isocyanate, cyanate,            carboxylate, oxalate, nitrate, nitrosyl, hydrogensulfate,            phosphate, dihydrogenphosphate, hydrogenphosphate or            hydrogencarbonate,        -   L is a water-miscible ligand chosen from the group            consisting of alcohols, aldehydes, ketones, ethers,            polyethers, esters, polyesters, polycarbonate, ureas,            amides, primary, secondary and tertiary amines, ligands with            pyridine nitrogen, nitriles, sulfides, phosphides,            phosphites, phosphines, phosphonates and phosphates,        -   k is a fraction or integer greater than or equal to zero,            and        -   P is an organic additive,        -   a, b, c, d, g and n are chosen such that the            electroneutrality of the compound (I) is ensured, where c            may be 0,        -   e is the number of ligand molecules, a fraction or integer            greater than 0, or 0,        -   f and h, independently of one another, are a fraction or            integer greater than 0, or 0.

Organic additives P which can be mentioned are: polyethers, polyesters,polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycolglycidyl ethers, polyacrylamide, poly(acrylamide-co-acrylic acid),polyacrylic acid, poly(acrylamide-co-maleic acid), polyacrylonitrile,polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ether,polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol,poly-N-vinylpyrrolidone, poly(N-vinylpyrrolidone-co-acrylic acid),polyvinyl methyl ketone, poly(4-vinylphenol), poly(acrylicacid-co-styrene), oxazoline polymers, polyalkyleneimines, maleic acidand maleic anhydride copolymers, hydroxyethylcellulose, polyacetates,ionic surface-active and interface-active compounds, bile acid or saltsthereof, esters or amides, carboxylic esters of polyhydric alcohols andglycosides.

These catalysts may be crystalline or amorphous. When k is zero,crystalline double-metal cyanide compounds are preferred. When k isgreater than zero, either crystalline, partially crystalline or elsesubstantially amorphous catalysts are preferred.

There are various preferred embodiments of the modified catalysts. Onepreferred embodiment covers catalysts of the formula (I) in which k isgreater than zero. The preferred catalyst then comprises at least onedouble-metal cyanide compound, at least one organic ligand and at leastone organic additive P.

In another preferred embodiment, k is zero, e is optionally also zeroand X is exclusively a carboxylate, preferably formate, acetate andpropionate. Such catalysts are described in WO 99/16775. In thisembodiment, preference is given to crystalline double-metal cyanidecatalysts. Also preferred are double-metal cyanide catalysts asdescribed in WO 00/74845, which are crystalline and platelet-like.

In a preferred embodiment, the present invention therefore provides aprocess in which the double-metal cyanide compound used as catalyst iscrystalline.

The modified catalysts are prepared by combining a metal salt solutionwith a cyanometallate solution, which may optionally contain both anorganic ligand L and also an organic additive P. Subsequently, theorganic ligand and optionally the organic additive are added. In apreferred embodiment of the catalyst preparation, an inactivedouble-metal cyanide phase is firstly prepared, and this is thenconverted into an active double-metal cyanide phase byrecrystallization, as described in PCT/EP01/01893.

In another preferred embodiment of the catalysts, f, e and k do notequal zero. These are double-metal cyanide catalysts which contain awater-miscible organic ligand (generally in amounts of from 0.5 to 30%by weight) and an organic additive (generally in amounts of from 5 to80% by weight), as described in WO 98/06312. The catalysts can either beprepared with vigorous stirring (24 000 rpm using Turrax) or withstirring, as described in U.S. Pat. No. 5,158,922.

Particularly suitable catalysts for the alkoxylation are double-metalcyanide compounds which contain zinc, cobalt or iron or two thereof.Prussian blue, for example, is particularly suitable.

Preference is given to using crystalline DMC compounds. In a preferredembodiment, a crystalline DMC compound of the Zn—Co type which compriseszinc acetate as further metal salt component is used as catalyst. Suchcompounds crystallize in monoclinic structure and have a platelet-likehabit. Such compounds are described, for example, in WO 00/74845 orPCT/EP01/01893.

DMC compounds suitable as catalysts may, in principle, be prepared byall ways known to the person skilled in the art. For example, the DMCcompounds can be prepared by direct precipitation, incipient wetnessmethod, by preparing a precursor phase and subsequent recrystallization.

The DMC compounds can be used as powder, paste or suspension, or bemolded to give a shaped body, be converted to moldings, foams or thelike, or be applied to moldings, foams or the like.

The catalyst concentration used for the alkoxylation, based on the finalquantity structure, is typically less than 2000 ppm (i.e. mg of catalystper kg of product), preferably less than 1000 ppm, in particular lessthan 500 ppm, particularly preferably less than 100 ppm, for exampleless than 50 ppm or 35 ppm, especially preferably less than 25 ppm.

In a preferred embodiment, the present invention provides a process inwhich the double-metal cyanide compound is used in an amount of 100 ppmor less, based on the final quantity structure.

In further embodiments, the present invention provides a process whereat least one of the following properties is satisfied:

-   -   (1) M¹ is chosen from the group Zn²⁺, Fe²⁺, Fe³⁺, Co³⁺, Ni²⁺,        Mn²⁺, Co²⁺;    -   (2) M² is chosen from the group Fe²⁺, Fe³⁺, Co³⁺,        or particularly preferably a process where M¹ is Zn²⁺and M² is        Co³⁺.

Suitable starter compounds are all compounds which have an activehydrogen. According to the invention, preferred starting compounds areOH-functional compounds.

Especially preferred starter compounds are monofunctional orpolyfunctional alcohols having 2 to 24 carbon atoms, especiallymonofunctional linear or once or more branched alkanols with 2 to 24carbon atoms.

Suitable branched alcohols are for example alcohols with a hydroxylgroup in the 2-, 3-, 4-position etc. The alkyl group may be linear oronce again branched and carry for example methyl or ethyl substituents.Examples of suitable alcohols are 2-decanol, 2-dodecanol,2-tetradecanol, 2-hexadecanol, each alcohol being obtainable by addingwater to an α-olefine, (6-ethyl)-3-nonanol, obtainable by reaction of2-ethylhexanol with acetone and subsequent hydrogenation of2-hexadecanol respectively 2-octa-decanol, obtainable by reaction of aC₁₃/C₁₅-aldehyd with acetone, 3-nonadecanol respectively(3-methyl)-2-octadecanol, (3-metyhl)-2-hexadecanol, 3-heptadecanol,obtainable by reaction of a C₁₃/C₁₅-aldehyd with 2-butanone. Thereaction products are based C₁₃/C₁₅-aldehyd are in a technical mixturebranched in α-position for approximately 40 to 50%.

Examples of further suitable alcohols are linear C₁₂-C₁₄-alkanes with ahydroxyl group in an none-terminal position of the chain or mixturesthereof (for example Saftanol®-alcohols of Nippon Shokubai orTergitol®-alcohols of Dow).

Starter compounds which can be used in the process according to theinvention are, in particular, monofunctional alcohols having 6 to 18carbon atoms, preferably alcohols having 8 to 15 carbon atoms, such as,for example, tridecanol or propylheptanol.

Alcohols suitable according to the invention are thus, in particular,octanol, 2-ethylhexanol, nonanol, decanol, undecanol, dodecanol,2-butyloctanol, tridecanol, tetradecanol, pentadecanol, isooctanol,isononanol, isodecanol, isoundecanol, isododecanol, isotridecanol,isotetradecanol, isopentadecanol, preferably isodecanol,2-propylheptanol, tridecanol, isotridecanol or mixtures of C13- toC15-alcohols or mixtures of 2-propylheptanol with structurally isomericC₁₀-alcohols.

The present invention therefore also provides, in a preferredembodiment, a process in which the starter compound is a monofunctionallinear or branched alcohol having 2 to 24, preferably 8 to 15 carbonatoms.

For example, the alcohols used according to the invention as startercompound are Guerbet alcohols, in particular ethylhexanol,propylheptanol, butyloctanol. The present invention therefore alsoprovides, in a particularly preferred embodiment, a process where thestarter compound is a Guerbet alcohol.

The alcohols used as starter compound may, according to the invention,also be mixtures of different isomers. For example, propylheptanol canbe obtained starting from valeraldehyde by aldol condensation andsubsequent hydrogenation. The preparation of valeraldehyde and thecorresponding isomers takes place by hydroformylation of butene, asdescribed, for example, in U.S. Pat. No. 4,287,370; Beilstein E IV 1, 3268, Ullmanns Encyclopedia of Industrial Chemistry, 5th edition, VolumeA1, pages 323 and 328. The subsequent aldol condensation is described,for example, in U.S. Pat. No. 5,434,313 and Römpp, Chemie Lexikon, 9thedition, keyword “Aldol addition” page 91. The hydrogenation of thealdol condensation product follows general hydrogenation conditions.

Furthermore, 2-propylheptanol can be prepared by condensation of1-pentanol (as a mixture of the corresponding methyl-1-butanols) in thepresence of KOH at elevated temperatures, see e.g. Marcel Guerbet, C. R.Acad Sci Paris 128, 511, 1002 (1899). Furthermore, reference is made toRbmpp, Chemie Lexikon, 9th edition, Georg Thieme Verlag Stuttgart, andthe citations given therein, and also Tetrahedron, Vol. 23, pages 1723to 1733.

In addition, secondary alcohols or mixtures are also suitable. These maybe obtainable, for example, by the addition of ketones onto aldehydeswith subsequent hydrogenation, as described in DE 100 35 617.6.Preference is given here to methyl ketones, such as acetone, methylethyl ketone or methyl isobutyl ketone. Also suitable are paraffinoxidation products which are formed, for example, by Bashkirovoxidation. Here, products of C₁₁-C₁₆-paraffin mixtures, particularlyproducts of C₁₂-C₁₄-paraffin mixtures, are preferred. Suitable alcoholsare also, for example, secondary alcohols, which are obtained byaddition of water onto olefins or by free-radical or other oxidation ofolefins.

The alkylene oxide mixture used in the process according to theinvention can, as well as ethylene oxide, comprise further alkyleneoxides, in particular a further alkylene oxide chosen from the groupconsisting of propylene oxide, butylene oxide and pentylene oxide.

In this case, for the purposes of the present invention, the alkyleneoxide mixtures preferably have an ethylene oxide fraction of more than50% (% by mass), in particular of more than 75%, particularly preferablyof more than 95%, for example of more than 99%.

In a preferred embodiment, according to the invention, no furtheralkylene oxide is used alongside ethylene oxide.

The present invention therefore provides, in a further embodiment, aprocess where the alkylene oxide mixture comprises ethylene oxide and afurther alkylene oxide chosen from the group consisting of propyleneoxide, butylene oxide and pentylene oxide.

In a further embodiment, the present invention thus also provides aprocess in which no further alkylene oxide is used alongside ethyleneoxide.

Preferably, the alkylene oxide mixture is used in the process accordingto the invention in amounts such that the resulting degree ofalkoxylation is, for example, in the range from 2 to 20, preferably inthe range from 3 to 14.

Moreover, the present invention also provides alkoxylates obtainable bythe above-described process.

The alkoxylates according to the invention exhibit good wetting on hardsurfaces. The advantageous wetting behavior of the mixtures according tothe invention can be determined, for example, by measurements of thecontact angle on glass, polyethylene oxide or steel. The alkoxylatesaccording to the invention further exhibit good emulsifying behaviorcombined with easy biodegradability.

The present invention thus also provides for the use of an alkoxylateaccording to the invention, in particular an ethoxylate, or analkoxylate prepared by a process according to the invention, inparticular an ethoxylate, as emulsifier, foam regulator or as wettingagent for hard surfaces, in particular for use in detergents, surfactantformulations for the cleaning of hard surfaces, humectants, cosmetic,pharmaceutical and crop protection formulations, paints, coatingcompositions, adhesives, leather-degreasing compositions, formulationsfor the textile industry, fiber processing, metal processing, foodindustry, water treatment, paper industry, fermentation or mineralprocessing and in emulsion polymerizations.

In addition, the alkoxylates prepared according to the invention serveto reduce the interfacial tension, for example in aqueous surfactantformulations. The reduced interfacial tension can, for example, bedetermined by the pendant-drop method. This also results in a bettereffect of the alkoxylates according to the invention as emulsifier orcoemulsifier. The alkoxylates according to the invention can also beused for reducing the interfacial tension in short times of customarilyless than one second, or for accelerating the establishment of theinterfacial tension in aqueous surfactant formulations.

Preferred fields of use for the alkoxylates according to the inventionare described in more detail below.

The alkoxylates according to the invention are preferably used in thefollowing fields:

-   -   Surfactant formulations for the cleaning of hard surfaces:        suitable surfactant formulations which can be additized with the        alkoxylates according to the invention are described, for        example, in Formulating Detergents and Personal Care Products by        Louis Ho Tan Tai, AOCS Press, 2000.    -   They comprise, for example, as further components, soap, anionic        surfactants, such as LAS or paraffinsulfonates or FAS or FAES,        acid such as phosphoric acid, amidosulfonic acid, citric acid,        lactic acid, acetic acid, other organic and inorganic acids,        solvents, such as ethylene glycol, isopropanol, complexing        agents, such as EDTA, NTA, MGDA, phosphonates, polymers, such as        polyacrylates, copolymers of maleic acid-acrylic acid, alkali        donors, such as hydroxides, silicates, carbonates, perfume oils,        oxidizing agents, such as perborates, peracids or        trichloroisocyanuric acid, Na or K dichloroisocyanurates,        enzymes; see also Milton J. Rosen, Manilal Dahanayake,        Industrial Utilization of Surfactants, AOCS Press, 2000 and        Nikolaus Schönfeldt, Grenzflächenaktive Ethylenoxidaddukte        [Interface-active ethylene oxide adducts]. This also covers, in        principle, formulations for the other applications mentioned.        They may be household cleaners, such as all-purpose cleaners,        dishwashing detergents for manual and automatic dishwashing,        metal degreasing, industrial applications, such as cleaners for        the food industry bottlewashing etc. They may also be printing        roll and printing plate cleaners in the printing industry.        Suitable further ingredients are known to the person skilled in        the art.    -   Humectants, in particular for the printing industry.    -   Cosmetic, pharmaceutical and crop protection formulations.        Suitable crop protection formulations are described, for        example, in EP-A-0 050 228. Further ingredients customary for        crop protection compositions may be present.    -   Paints and coating compositions, dyes, pigment preparations and        adhesives in the coatings and polymer film industry.    -   Leather-degreasing compositions.    -   Formulations for the textile industry, such as leveling agents        or formulations for yarn cleaning.    -   Fiber processing and auxiliaries for the paper and pulp        industry.    -   Metal processing, such as metal finishing and electroplating        sector.    -   Food industry.    -   Water treatment and production of drinking water.    -   Fermentation.    -   Mineral processing and dust control.    -   Building auxiliaries.    -   Emulsion polymerization and preparation of dispersions.    -   Coolants and lubricants.

Such formulations usually comprise ingredients such as surfactants,builders, fragrances and dyes, complexing agents, polymers and otheringredients. Typical formulations are described, for example, in WO01/32820. Further ingredients suitable for various applications aredescribed, for example, in EP-A-0 620 270, WO 95/27034, EP-A-0 681 865,EP-A-0 616 026, EP-A-0 616 028, DE-A-42 37 178 and U.S. Pat. No.5,340,495 and in Schönfeldt, see above.

Generally, the alkoxylates according to the invention can be used in allfields in which the action of interface-active substances is necessary.

The present invention therefore also provides detergents, cleaners,wetting agents, coating compositions, adhesive compositions,leather-degreasing compositions, humectants or textile-treatmentcompositions or cosmetic, pharmaceutical or crop protection formulationcomprising an alkoxylate according to the invention or an alkoxylateprepared by a process according to the invention. The products herepreferably comprise 0.1 to 20% by weight of the alkoxylates.

The present invention will be illustrated in more detail below byreference to examples.

EXAMPLES Preparation Example Double-metal Cyanide Catalyst

16000 g of aqueous hexacyanocobaltic acid (cobalt content: 9 g/l) wereinitially introduced into a stirred vessel with a volume of 30 1 andequipped with a propeller stirrer, immersion tube for the meteredaddition, pH probe and scattered light probe, and heated to 50° C. withstirring. Then, with stirring at a stirrer output of 0.4 W/1, 9224 g ofaqueous zinc acetate dihydrate solution (zinc content: 2.6% by weight),which had likewise been heated to 50° C., were introduced over thecourse of 15 minutes.

351 g of Pluronic® PE 6200 (BASF AG) were added to this precipitatesuspension, and the mixture was stirred for a further 10 minutes.

Then, a further 3690 g of aqueous zinc acetate dihydrate solution (zinccontent: 2.6% by weight) were metered in over the course of 5 minuteswith stirring with a stirring energy of 1 W1.

The suspension was after-stirred for two hours. During this period, thepH dropped from 4.02 to 3.27 and then remained constant. The precipitatesuspension obtained in this way was then filtered off and washed on thefilter with 6 times the cake volume of water.

The moist filtercake was dried and dispersed in Tridekanol® N by meansof a gap rotor mill. The suspension obtained had a multimetal cyanidecontent of 5% by weight.

Example 1 Comparative Example, 2-propylheptanol+8 EO at a Maximum TotalPressure of 1.70 Bar

316 g (2.0 mol) of 2-propyl-1-heptanol (isomer mixture of 87%2-propyl-1-heptanol, 11% of 2-propyl-4-methyl-1-hexanol, <1%2-propyl-5-methyl-1-hexanol) and 35 ppm of double-metal cyanide catalyst(based on the product) were dewatered at a temperature of 100° C. andabout 20 mbar for two hours in a 3.5 1 pressure autoclave. The systemwas then flushed with nitrogen three times and a temperature of 140° C.was set. After the temperature had been reached, a total of 704 g (16.0mol) of ethylene oxide were to be metered in, with stirring, at amaximum total pressure of 1.70 bar (absolute). Following the addition of582 g of ethylene oxide, a reaction could no longer be detected(virtually no pressure decrease, virtually no evolution of heat).

Example 2 Starting the Reaction With Pressure Increase

The reaction mixture from Example 1 was stirred further and the totalpressure increased to 6.0 bar by adding ethylene oxide. An adequatepressure decrease and temperature increase could again be detected,meaning that the remaining amount of ethylene oxide could be reactedsuccessfully.

When the metered addition of ethylene oxide was complete, the mixturewas stirred for a further 1 h at 140° C., then cooled to 80° C., and thereactor was flushed three times with nitrogen, then evacuated to 20 mbarto degas, and emptied. The reaction product was not filtered andcorresponded to the desired product.

Example 3 Comparative Example, 2-propylheptanol+1.2 PO+6 EO at a MaximumEO Pressure of 1.70 Bar

316 g (2.0 mol) of 2-propyl-1-heptanol and 35 ppm of double-metalcyanide catalyst (based on the product) were dewatered at a temperatureof 100° C. and about 20 mbar for two hours in a pressure autoclave. Thesystem was subsequently flushed three times with nitrogen and thenheated to 140° C. After the temperature had been reached, a total of 140g (2.4 mol) of propylene oxide were metered in, with stirring, at 140°C. When the PO metered addition was complete, the mixture was stirredfor a further 15 minutes at 140° C.

The temperature is held at 140° C., and then 528 g (12.0 mol) ofethylene oxide were metered in at a maximum total pressure of 1.70 bar.Following the addition of 424 g of ethylene oxide, an adequate reactioncould no longer be detected (virtually no pressure decrease, virtuallyno evolution of heat).

Example 4 Starting the Reaction with Pressure Increase

The reaction mixture from example 3 was further stirred and the totalpressure increased to 6.0 bar by adding ethylene oxide. An adequatepressure decrease and temperature increase could again be detected,meaning that the remaining amount of ethylene oxide could be reactedsuccessfully.

When the metered addition of ethylene oxide was complete, the mixturewas stirred for a further 1 h at 140° C., then cooled to 80° C., and thereactor was flushed three times with nitrogen, then evacuated to 20 mbarto degas, and emptied. The reaction product was not filtered andcorresponded to the desired product.

Example 5 2-propylheptanol+8 EO at a Maximum EO Pressure of 2.5 Bar

316 g (2.0 mol) of 2-propyl-1-heptanol and 35 ppm of double-metalcyanide catalyst (based on the product) were dewatered at a temperatureof 100° C. and about 20 mbar for two hours in a pressure autoclave. Thesystem was then flushed three times with nitrogen and then a totalpressure of 2.5 bar of nitrogen (absolute) at 140° C. was established.After the temperature had been reached, a total of 704 g (16.0 mol) ofethylene oxide were metered in, with stirring, at a maximum totalpressure of 5.0 bar (absolute). When the metered addition of ethyleneoxide was complete, the mixture was stirred for a further 1 h at 140°C., then cooled to 80° C., and the reactor was flushed three times withnitrogen, then evacuated to 20 mbar to degas, and emptied. The reactionproduct was not filtered and corresponded to the desired product.

Example 6 2-propylheptanol+1.2 PO+6 EO at a Maximum EO Pressure of 2.5Bar

316 g (2.0 mol) of 2-propyl-1-heptanol (isomer mixture of 87%2-propyl-1-heptanol, 11% 2-propyl-4-methyl-1-hexanol, <1%2-propyl-5-methyl-1-hexanol) and 35 ppm of double-metal cyanide catalyst(based on the product) were dewatered at a temperature of 100° C. andabout 20 mbar for two hours in a pressure autoclave. The system wassubsequently flushed three times with nitrogen and then heated to 140°C. After the temperature had been reached, a total of 140 g (2.4 mol) ofpropylene oxide were metered in, with stirring, at 140° C. When the POmetered addition was complete, the mixture was stirred for a further 15minutes at 140° C.

A total pressure of 2.5 bar of nitrogen (absolute) at 140° C. was thenestablished and afterwards the metered addition of a total of 528 g(12.0 mol) of ethylene oxide at a maximum total pressure of 5.0 bar(absolute, 140° C.) was started. When the metered addition of ethyleneoxide was complete, the mixture was stirred for a further 1 h at 140°C., then cooled to 80° C., and the reactor was flushed three times withnitrogen, then evacuated to 20 mbar to degas, and emptied. The reactionproduct was not filtered and corresponded to the desired product.

1. A process for the preparation of at least one alkoxylate comprising:bringing into contact an alkylene oxide mixture comprising ethyleneoxide with at least one starter compound in the presence of at least onedouble-metal cyanide compound of the formula 1:M¹ _(a)[M²(CN)_(b)(A)_(c)]_(d)·fM¹ _(g)X_(n)·h(H2O)·eL·kP. wherein M¹ isa metal ion selected from the group consisting of Zn²⁺, Fe³⁺, Co³⁺,Ni²⁺, Mn²⁺, Co²⁺, Sn²⁺, Pb²⁺, Mo⁴⁺, Mo⁶⁺, Al³⁺, V⁴⁺, V⁵⁺, Sr²⁺, W⁴⁺,W⁶⁺, Cr²⁺, Cr³⁺, Cd²⁺, Hg²⁺, Pd²⁺, Pt²⁺, V²⁺, Mgt⁺, Ca²⁺, Ba²⁺, Cu²⁺,La³⁺, Ce³⁺, Ce⁴⁺, Eu³⁺, Ti³⁺, Ti⁴⁺, Ag⁺, Rh²⁺, Rh³⁺, Ru²⁺, and Ru³⁺; M²is a metal ion selected from the group consisting of Fe²⁺, Fe³⁺, Co²⁺,Co³⁺, Mn²⁺, Mn³⁺, V⁴⁺, V⁵⁺, Cr²⁺, Cr³⁺, Rh³⁺, Ru²⁺, and Ir³⁺; A and X,independently of one another, are anions, each of which is selected fromthe group consisting of halide, hydroxide, sulfate, carbonate, cyanide,thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate,nitrosyl, hydrogensulfate, phosphate, dihydrogenphosphate,hydrogenphosphate or and hydrogencarbonate; L is a water-miscible lagandselected from the group consisting of alcohols, aldehydes, ketones,ethers, polyethers, esters, polyesters, polycarbonate, ureas, amides,primary, secondary and tertiary amines, ligands with pyridine nitrogen,nitriles, sulfides, phosphides, phosphates, phosphines, phosphonates andphosphates; k is a fraction or an integer, wherein the value of k isgreater than or equal to zero; P is at least one organic additiveselected from the group consisting of polyethers, polyesters,polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycolglycidyl ethers, polyacrylamide, poly(acrylamide-co-acrylic acid),polyacrylic acid, poly(acrylamide-co-maleic acid), polyacrylonitrile,polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ether,polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol,poly-N-vinylpyrrolidone, poly(N-vinylpyrrolidone-co-acrylic acid),polyvinyl methyl ketone, poly(4-vinylphenol), poly(acrylicacid-co-styrene), oxazoline polymers, polyalkyleneimines, maleic acidand maleic anhydride copolymers, hydroxyethylcellulose, polyacetates,ionic surface-active and interface-active compounds, bile acid or saltsthereof, esters or amides, carboxylic esters of polyhydric alcohols, andglycosides; a, b, c, d, g and n are chosen such that theelectroneutrality of the compound I is ensured; e is the number ofligand molecules, wherein e is a fraction or an integer, and wherein thevalue of e is greater than or equal to 0; and each of f and h,independently of one another, is a fraction or an integer wherein eachoff and h, independently of each other, has a value greater than orequal to 0; wherein, during the induction phase, the sum of the inertgas partial pressure and the ethylene oxide partial pressure is 1.5 barto 6.0 bar; and wherein the starter compound is a Guerbet alcohol. 2.The process of claim 1, wherein the total pressure does not exceed 11bar over the course of the reaction.
 3. The process of claim 1, wherein:(1) M¹ is selected from the group consisting of Zn²⁺, Fe²⁺, Fe³⁺, Co³⁺,Ni²⁺, Mn²⁺ and Co²⁺; or (2) M² is selected from the group consisting ofFe^(e+), Fe³⁺, and Co³⁺.
 4. The process of claim 1, wherein M¹ is Zn²⁺and M² is Co³⁺.
 5. The process of claim 1, wherein the double-metalcyanide compound catalyst is crystalline.
 6. A process for thepreparation of at least one alkoxylate comprising: bringing into contactan alkylene oxide mixture comprising ethylene oxide with at least onestarter compound in the presence of at least one double-metal cyanidecompound of the formula 1:M¹ _(a)[M²(CN)_(b)(A)_(c)]_(d)·fM¹ _(g)X_(n)·h(H2O)·eL·kP. wherein M¹ isa metal ion selected from the group consisting of Zn²⁺, F³⁺, Co³⁺, Ni²⁺,Mn²⁺, Co²⁺, Sn²⁺, Pb²⁺, Mo⁴⁺, Mo⁶⁺, Al³⁺, V⁴⁺, V⁵⁺, Sr²⁺, W⁴⁺, W⁶⁺,Cr²⁺, Cr³⁺, Cd²⁺, H²⁺, Pd²⁺, Pt^(2+, V) ²⁺, Mgt⁺, Ca²⁺, Ba²⁺, Cu²⁺,La³⁺, Ce³⁺, Ce⁴⁺, Eu³⁺, Ti³⁺, Ti⁴⁺, Ag⁺, Rh²⁺, Rh³⁺, Ru²⁺, and Ru³⁺; M²is a metal ion selected from the group consisting of Fe²⁺, Fe³⁺, Co²⁺,Co³⁺, Mn²⁺, Mn³⁺, V⁴⁺, V⁵⁺, Cr²⁺, Cr³⁺, Rh³⁺, Ru²⁺, and Ir³⁺; A and X,independently of one another, are anions, each of which is selected fromthe group consisting of halide, hydroxide, sulfate, carbonate, cyanide,thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate,nitrosyl, hydrogensulfate, phosphate, dihydrogenphosphate,hydrogenphosphate or and hydrogencarbonate; L is a water-miscible lagandselected from the group consisting of alcohols, aldehydes, ketones,ethers, polyethers, esters, polyesters, polycarbonate, ureas, amides,primary, secondary and tertiary amines, ligands with pyridine nitrogen,nitriles, sulfides, phosphides, phosphates, phosphines, phosphonates andphosphates; k is a fraction or an integer, wherein the value of k isgreater than or equal to zero; P is an organic additive, a, b, c, d, gand n are chosen such that the electroneutrality of the compound I isensured; e is the number of ligand molecules, wherein e is a fraction oran integer, and wherein the value of e is greater than or equal to 0;and each of f and h, independently of one another, is a fraction or aninteger wherein each off and h, independently of each other, has a valuegreater than or equal to 0; wherein, during the induction phase, the sumof the inert gas partial pressure and the ethylene oxide partialpressure is 1.5 bar to 6.0 bar, and wherein the starter compound is aGuerbet alcohol, wherein the alkylene oxide mixture has an ethyleneoxide fraction of more than 99%.
 7. An alkoxylate obtained by theprocess of claim
 1. 8. The process of claim 1, wherein c has a value of0.
 9. The process of claim 1, wherein (1) M¹ is selected from the groupconsisting of Zn²⁺, Fe³⁺, Fe⁺, Co³⁺, Ni²⁺, Mn²⁺ and Co²⁺; and (2) M² isselected from the group consisting of Fe²⁺, Fe³⁺, and Co³⁺.
 10. Theprocess of claim 1, wherein the alkylene oxide mixture has an ethyleneoxide fraction of more than 99%.
 11. The process of claim 1, wherein eis greater than zero.
 12. The process of claim 1, wherein f is greaterthan zero.
 13. The process of claim 1, wherein g is greater than zero.14. The process of claim 1, wherein k is greater than zero.
 15. Theprocess of claim 1, wherein e is zero.
 16. The process of claim 1,wherein f is zero.
 17. The process of claim 1, wherein g is zero. 18.The process of claim 1, wherein k is zero.